Fungicide



Patented Mar. 4, 1941 I PATENT OFFICE FUNGICIDE Lawrence H. Flett, Hamburg, N. Y., assignor to National Aniline 8; Chemical Company, Inc.,

New York, N. Y., a corporation of New York.

No Drawing. Application July 31, 1936, Serial No. 93,718

6 Claims.

--This invention relates to fungicidal compositions of matter and their use as fungicides. The compositions of this invention are especially suitable for application to plants, trees, shrubs, and the like to free and protect the same from plant diseases and fungi.

In my applications Serial Nos. 691,081 and 691,082, filed September 26, 1933, I have disclosed sulfonated aromatic compounds of the type AHRS (wherein A represents an aromatic nucleus; i. e.', an aromatic nucleus which may contain only the groups represented by H, R, and S as substituents or which may contain additional substituents, H represents a nuclear hydroxyl group, R represents a nuclear alkyl group containing at least 12 carbon atoms, and S represents a nuclear sulfonic acid group in the free acid or salt form), and especially alkyl phenol sulfonic acid compounds which correspond with the general formula in which X represents hydrogen or a methyl group, R represents a nuclear alkyl hydrocarbon radical (saturated or unsaturated) containing 12 or more carbon atoms, and M represents hydrogen or a metal, particularly an alkali metal, or an ammonium or organic ammonium radical.

Further, in my application Serial No. 737,777, filed July 31, 1934, which has issued as United States Patent No. 2,196,985, I have disclosed products of the type AHRS in which the alkyl group represented by R is derived from a petroleum distillate boiling between 80 C. at atmospheric pressure and 380 C. at mm. pressure, and especially mixed products of the said type.

. According to the present invention, alkyl aromatic sulfonates of the type ARS (in which A, R and S have the meaning defined above), particularly the said sulfonated alkyl hydroxy aromatic compounds of the type AI-IRS, and especially those derived from phenol or a cresol, preferably by condensation with a halogenated hydrocarbon mixture of the type of Pennsylvania petroleum distillates, are employed per se as fungicides. The fungicidal compositions of this invention comprise any one or a mixture of nuclearly alkylated aromatic sulfonic acids or their" salts in which the aryl nucleus has at least one nuclear substituent alkyl group which contains at least 7 carbon atoms. The aryl nucleus may be monoor polycyclic and can contain other substituents in addition to the essential C-alkyl group and C-sulfo group.

I have found that the said sulfonated products, particularly those derived from halogenated hydrocarbon mixtures of the typeof Pennsylvania petroleum distillates disclosed in my Patent No. 2,196,985, are valuable parasiticides which are characterized by effective parasiticidal action in addition to wetting and spreading power. The term parasiticides. as' employed herein denotes collectively fungicides, insecticides, insectifuges, and vermicides. As a result they can be employed in concentrations in aqueous or other solutions and dispersions or powders in low concentrations. Thus, they are effective in aqueous solutions of a concentration on the order of 0.01% to 5% of said sulfonate. They are ordinarily applied in concentrations of 0.1% to 1-0% and, in general, 0.5% of said sulfonate. They are highly effective both against insects controlled by contact poisons and by stomach poisons, since they act both as contact and as stomach poisons, and further are effective for the control of most fungi including those controlled by copper compounds and those controlled by sulfur. Many of the organic ammonium salts are of relatively low solubility'in water and are of an adherent nature which renders them of value in the control of parasites on vegetation.

The compositions of the present invention have the further advantage that the said alkyl aromatic sulfonates when combined with nonpoisonous metals or bases such as the alkali metals, are sufficiently non-toxic to warm-bloodpreferably an open-chain hydrocarbon radical.

Preferred compounds employed in accordance with the present invention are the mixed alkyl derivatives of aromatic sulfonic acids of the benzene series (i. e., aromatic sulfonic acids containing a single benzene nucleus), especially mixed alkyl derivatives of phenol and cresol sulfonic acids, in which the alkyl groups correspond with the aliphatic hydrocarbons of petroleum distillates and similar products boiling mainly above 170 C. at atmospheric pressure, more particularly between 170 C. at atmospheric pressure and 215 C. at 50 mm. pressure and especially between 215 C. and 300 C. (both at atmospheric pressure), and especially aliphatic hydrocarbon mixtures of the Pennsylvania petroleum kerosene type, of said boiling characteristics, which are obtainable by halogenation of the said petro- .u leum distillate or similar products, followed by condensation of resulting mixed alkyl halides.

with the corresponding aromatic compound, preferably with the aid of a metal halide condensing agent, and sulfonation of resulting mixed alkyl derivatives of the aromatic compound, as disclosed in my Patent No. 2,196,985 In those cases where it is desired to employ an insoluble form of the sulfonate in an aqueous medium,-a water-soluble form of the same or of another sul'fonate of the said type can be employed to disperse the whereby the advantageous properties of both forms come into play. The soluble alkyl aryl sulfonates can be mixed mechanically with the insoluble amine salts of the alkyl aryl sulfonates, or the amine salts and soluble sulfonates can be incorporated in a water suspension-or solution, or in a solution in an organic solvent. The liquid phase of the dispersion or solution can then The alkyl aromatic sulfonates may be employed in. accordance with the present invention in the form of their free sulfonic acids or in-the form of salts of metals (as for example, of the alkali metals) or of organic bases, or of ammonia, etc. The salts may be obtained in any suitable manner; for example by reacting the alkyl aromatic sulfonic acid, either in the crude form resulting from the sulfonation of the corresponding alkyl aromatic compound or in a purified form, with a. metal oxide or hydroxide or an organic base, or of a suitable salt of one of 5 these, preferably in an amount adapted to form a neutral product.

The organic amines which may be used for neutralizing the alkyl aryl sulfonic acids to form the amine salts of the compositions of this invention can be aliphatic, aromatic or hetero- ,cyclic. They are preferably free from saltforming groups, such as sulfonic or carboxylic groups. The preferred amines form salts with the sulfonated alkyl aryl compounds which are -0 insoluble or slightly, soluble in water, and, therefore, resist removal by water, for example, rain. Their dispersions retain the toxic characteristics of the amines and the spreading, wetting and penetrating qualities of the alkyl aryl sulfonates.

Among the bases, oxides and salts which may be employed to produce salts useful in accordance with the present invention, are, for 'example, sodium, potassium and ammonium hydroxides; sodium, potassium carbonates and bicarbonates; ammonia; magnesium oxide; basic copper carbonate; ethylamine; mono-, diand tri-rpropylamin'es, -butyl amines, -amylamines, etc. pyridine; triethanolamine; propanolamines; butanolamines; diamino propanol, triethylene tetramine, quinafldine, aniline, toluiinsoluble sulfonate,

be-rejnoved by mechanical means or evapora-' dines, phenetidines, stearylamine, ethylene diamine, quinoidine, piperidine, cetylamine, nicotine, etc. Mixed amines also may be employed.

The invention will be illustrated by the following examples in connection with mixed alkyl phenol sulfonates obtained from a Pennsylvania kerosene. distillate as disclosed in Exa'mple 24 of Patent No. 2,196,985. According to this example a mixture of alkyl derivatives of phenol, in which the alkyl groups are derived from the kerosene distillate, is sulfonated and the sulfonation mixture is neutralized. For convenience the unneutralized sulfonation product will be referred to herein as kerosene phenol sulfonic acid. It will be understood that the invention is not limited thereto and that others of the alkyl aromatic sulfonates of the present invention canbe similarly employed. The parts are by weight.

EXAMPLE 1' The sodium salt of kerosene phenol sulfonic" acid, free from inorganic sulfates, is dissolved I in water. tion as an insecticide is shown in the following tables.

I. Insecticide by spraying as contact poison Percent Parasite concen- Perfmnt Tune m nation kill hours Aphia pomi 0. 5 99:2 48 Do 0. 125 98. 5 24 Apllia spirecolm 25 96. 3 24 Anasa trietia 0. 5 48 Leptinotarac decimlineata (Colorado potato beetle) 0. 5 70 48 Aster lace fly 0. 6 97 48 II. Insecticide by spraying leaves (Stomach pozs' on) Percent I Parasite eoneem Percent Time in nation kill hours Leptino tarsa decimlimata 0. 25 56 24 Do 0. 25 63 48 0.25 X00 Control 0 48 Control 10 100 0.25 75 100 Control 5 100 The following table illustrates the eifect of varying acidity upon the insecticidal action of theproduct as a contact insecticide.

III.

Percent Percent Parasite eoncenpH kill in 48 tration hours Aphis 12mm 0. 05 2. 9 100 Do 0.05 4. 9 100 EXAMPLE, 2

The efiectiveness of the resulting soluaction of the produc s .of' above Examples 2 IV. insecticide by spraying-as contact poison Product of Percent Exam la Parasite concan- Pemnt Time in No. tntlon 2; Black ants 0.5 00 48- 5.. Aphil pomL- 0. 04 100 24 5. --..d0. 0.03 .6 24 5.. 0.02 as 24 Leziamurn decimlin- 0.6 100 24 I Aster lace fly 0. 3 100 48 uble. It is readily dispersed in aqueous solutions by water-soluble dispersing agents, as for example, the sodium alkyl aromatic sulfonates herein disclosed. For such dispersions, an amount of dispersing agent ranging irom about one quarter to an equal weight of the amine salt is sumcient. The amine salt is also soluble in organic solvents as, for example, benzene.

Aqueous compositions, which contain up to about 1 per cent by weight oi. these amine salts may be used as parasiticidal sprays for plants. without fear of phytocidal effects. The aqueous sprays wet and spread over the leaves and stems of the plants very rapidly and adhere in the form of thin continuous films.

EXAMPLE 3 EXAMPLE 4 An aqueous solution of the kerosene phenol sulfonic acid employed in above Example 2 is neutralized with a solution of quinoldlne in alcohol. (Quincidine" is the name applied to the mixture of alkaloid substances remaining aiter extraction of the more valuable and crystalline alkaloids from crude cinchona.) The mixture, after evaporating the alcohol, leaves a thick paste which is insoluble in water. 10 parts 01 this thick paste, 10 parts of a salt-free mixture of sodium kerosene phenol sulfonate, and about 20 parts of alcohol are thoroughly mixed, and the resulting paste is dried byevaporation of the alcohol. The dry residue can be dispersed in water easily to give milky emulsions which may be used as insecticidal sprays- Such emulsions containing up to 2 per cent of the dry mixture, are made quite readily.

ExlmPLz5 v I An aqueous solution of kerosene phenol sul- V'. Insecticide M spraying as stomach pots on Product of Percent P t Exam 1e Parasite concen- No. tration km ham 5 Arum trims 0.25 100 5 .-do Control 5 100 The following table illustrates the'iungicidal action of'alkyl aromatic sulfonates oi the present invention. In making these tests an aqueous solution of the sulfonate was sprayed onto a prepared plate, allowed to evaporate and spores oi the fungus under test were placed on the resulting plate and allowed to germinate.

VI. Fungicide control It will be realized by those skilled in the art that the invention is not limited by the. above examples. The present invention further includes the use as fungicides of mixtures of two or more ionic acid employed in above Example 2 is neutralized with commercial 95 per cent nicotine base, with the addition of suillcientalcohol to permit the neutralized mixture to be agitated thoroughly and easily. After neutralization, the alcohol is evaporated until the mixture is noninflammable.

The following table illustrates the insecticidal different alkyl aromatic suliionates of the type herein disclosed.

This application is a continuation-in-part of my application Serial No. 737,777, filed July 31, 1 34, now United States Patent No. 2,196,985.

claim:

1. A fungicidal composition adapted to control fungi of-the types controlled by copper compounds .and controlled by sulfur comprising a sulfonation product containing a mixture of sulfonated alkyl phenol compounds which difler from each other in the alkyl group, obtainable by halogenation of a petroleum distillatewhich bolls within the range C. to 300 C. at atmospheric pressure, condensation of the resulting halogenated product with a phenol compound selected from the group consisting of phenol and cresol to form a condensation product comprising a mixture of nuclearly alkylated phenol .com-,

pounds, and sulfonation of at least a portion of the resulting condensation product, saldsulionation product containing a member selected from the group consisting of the free sulionic acid group and salts of said group.

2. A fungicidal composition adapted to control fungi of the types controlled by copper and con-' trolled by sulfur comprising a sulfonation product containing a mixture of sultonated alkyl phenol compounds which differ from each other in the alkyl group, obtainable by the halogenation of as petroleum distillate which boils within the range 215 C. to 300 C. at atmospheric pressure, condensation of the resulting halogenated product with a phenol selected from the group consisting oi. phenol and cresol to form a condensation product comprising a mixture of nuclearly alkylated phenol compounds, and sulfonation 01' at least a portion of the resulting condensation product, saidsulfonation product being in the form of the sodium sulfonate.

3. A fungicidal composition containing as an essential fungicidal constituent a mixture of al-kyl phenol sulfonates oi the benzene series which difler from each other in the alkyl groups and wherein the alkyl group are derived from a petroleum distillate which boils mainly within the range 170'? to 300 C. at atmospheric pressure.

4. A process of controlling fungi on livingplants which comprises applying to the plant a fungicidal composition containing as an essential phenol compounds which'difler from each other in the alkyl group, obtainable by halogenation of a petroleum distillate which boils within the range 170 C. to 300 C. 'at atmospheric pressure, condensation of the resulting halogenated product with a phenol compoundselected from the group consisting of phenol and cresol to form a condensation product comprising a mixture of nuciearly alkylated phenol compounds, and sulfonation of at least a portion or the resulting condensation product, said sulfonation product containing a member selected from the class consisting of the free sulfonlc acid group and salts of said group. v

6. A process of controlling fungi on living plants which comprises applying to the plant a fungicidal composition adapted to control fungi of the types controlled by copper and controlled by sulfur comprising a sulfonatlon product containing a mixture of sulfonated alkyl phenol compounds which difier from each-other in the alkyl group, obtainable by the halogenation of a petroleum distillate which boils within the range 215 C. to

300 C. at atmospheric pressure, condensation of the resulting halogenated product with a phenol selected from the group consisting of phenol and cresoi to form a condensation product comprising a mixture of nuclearly aikylated phenol compounds, and sulfonation of at least a portion oi the resulting condensation product. said sulfona tion product being in the iorm of the sodium sulfonate.

LAWRENCE H. FLE'IT. 

